Continuous dyeing of polyester fibers with water-immiscible halogenated hydrocarbons and amino anthraquinone dyestuffs

ABSTRACT

Process for the continuous dyeing of synthetic fiber materials from organic solvents, characterised in that the fibre materials are impregnated with dyeing liquids which contain anthraquinone dyestuffs of formula   IN WHICH Hal represents chloro or bromo, X represents hydrogen, hydroxy, amino or acylamino and B represents alkyl, cycloalkyl or aralkyl and wherein m is a number from 0 - 2 and n a number from 0 - 3 and subjecting the fibre materials subsequently to a heat treatment. The dyeings obtained are distinguished by a high dyestuff yield, very good build-up and excellent fastness properties, especially very good fastness to thermofixing, washing, rubbing and light.

United States Patent [191 Neeff et al.

[ Aug. 21, 1973 CONTINUOUS DYEING OF POLYESTER FIBERS WITHWATER-IMMISCIBLE HALOGENATED HYDROCARBONS AND AMINO ANTHRAQUINONEDYESTUFFS [75] Inventors: Rutger Neeff, Leverkusen; Peter Wegner,Cologne; Volker l-lederich, Cologne; Robert Kuth, Cologne, all ofGermany [73] Assignee: Bayer Aktiengesellschaft,

Leverkusen, Germany [22] Filed: July 30, 1970 [21] Appl. No.: 59,727

[30] Foreign Application Priority Data Aug. 6, 1969 Germany P 19 39897.1

[52] US. Cl 8/39, 8/25, 8/94, 260/372, 260/378, 260/380, 260/381 [51]Int. Cl. C091) 1/02, C09b l/16, C09b l/56,

FOREIGN PATENTS OR APPLICATIONS 1,217,380 12/1970 Great Britain OTHERPUBLICATIONS White, ADR, 6-31-67, p. 18-24.

Primary Examiner-George F. Lesmes Assistant Examiner-Patricia C. lvesAtt0rneyPlumley and Tyner [57] ABSTRACT Process for the continuousdyeing of synthetic fiber materials from organic solvents, characterisedin that the fibre materials are impregnated with dyeing liquids whichcontain anthraquinone dyestuffs of formula (Hal)m in which Halrepresents chloro or bromo, X represents hydrogen, hydroxy, amino oracylamino and B represents alkyl, cycloalkyl or aralkyl and wherein m isa number from 0 2 and;n a number from 0 3 and subjecting the fibrematerials subsequently to a heat treat ment.

The dyeings obtained are distinguished by a high dyestuff yield, verygood build-up and excellent fastness properties, especially very goodfastness to thermofixing, washing, rubbing and light.

12 Claims, No Drawings CONTINUOUS DYEING OF POLYESTER FIBERS WITHWATER-IMMISCIBLE HALOGENATED HYDROCARBONS AND AMINO ANTHRAQUINONEDYESTUFFS The subject of the invention is a process for the continuousdyeing of the synthetic fibre materials from organic solvents; theprocess is characterised in that the fibre materials are impregnatedwith dyeing liquors which contain anthraquinone dyestuffs of formula NET)11 I l S- aDm in which Hal in particular denotes a chlorine or bromineatom,

X denotes a hydrogen atom, a hydroxyl, lower alkoxy, amino, loweralkylamino or cycloalkylamino group, an arylamino, especiallyphenylamino group which is optionally substituted by halogen atoms ortrifluoromethyl groups, an arylsulphonylamino group, alkylsulphonylaminogroup, a radical of formula or a radical of formula m is a number from O2, n is a number from O 3, p is a number from 0 3 and q is a number from0 2, and B and B independently of one another represent a C C alkyl,cycloalkyl or aralkyl radical.

with the proviso that the sum of the carbon atoms which are present intotal in the substituent B or in the substituents B and B is at least 1and at most 9 and the sum of n and p and q is at least 1, and that thefibre materials are subsequently subjected to a heat treatment.

As examples of B and B, there may be mentioned: as C C alkyl radicals,the methyl, ethyl, propyl, isopropyl, iso-butyl, sec.-butyl,tert.-butyl, iso-amyl, sec.- pentyl, neopentyl, methyl-pentyl,dimethyl-butyl, methyl-hexyl, dimethyl-pentyl, trimethyl-butyl,isooctyl, methyl-heptyl, dimethyl-hexyl, trimethyl-pentyl,tetra-methyl-butyl, iso-nonyl, dimethyl-heptyl and trimethyl-hexylradicals; as cycloalkyl radicals, the cyclohexyl and themethylcyclohexyl radicals and, as aralkyl radicals, especially thebenzyl and the a,adimethylbenzyl radical.

The dyestuffs used for the dyeing from organic solvents according to theinvention are obtained according to processes which are in themselvesknown, for example by reaction of l-amino-2- halogenanthraquinones,which may be appropriately substituted in the 4-position. withthiophenol and such thioaryl compounds as carry one or more alkyl.aralkyl or cycloalkyl radicals containing 1 9 carbon atoms. in thepresence of inorganic or organic bases.

Possible organic solvents for the process according to the invention arethose solvents which are essentially immiscible with water and of whichthe boiling points lie between 40 and 150 C, for example aromatichydrocarbons, such as toluene or xylene, aliphatic halogenatedhydrocarbons, especially chlorinated hydrocarbons, such as methylenechloride, chloroform, carbon tetrachloride, dichlorethane,trichlorethane, tetrachlorethane, dichloropropane, chlorobutane,dichlorobutane, as well as aliphatic fluoroand fluorochlorohydrocarbons,such as perfluoro-n-hexane, 1,2,- Z-trifluoro-trichlorethane andtrifluoropentachloropropane, and aromatic chloroand fluoro-hydrocarbonssuch as chlorobenzene, fluorobenzene, chlorotoluene andbenzotrifluoride.

Tetrachlorethylene, trichlorethylene, 1 ,l ,1- trichlorethane and1,1,l-trichloropropane have proved particularly suitable. Mixtures ofthese solvents can also be used.

The synthetic fibre materials to be dyed according to the process of theinvention are particularly fibre materials of polyesters, for examplepolyethylene terephthalates or polyesters of 1,4-bis-(hydroxymethyl)-cyclohexane and terephthalic acid, of cellulose triacetate, of syntheticpolyamides, such as poly-ecaprolactam, polyhexamethylenediamine adipateor poly-w-amiho-undecane-acld, of polyurethanes or of polyolefins. Thefibre materials can be in the form of woven fabrics or knitted fabrics.

For dyeing, the dyestuffs to be used according to the invention aredissolved in the organic solvents which are essentially immiscible withwater, or are added to these solvents in the form of solutions insolvents which are infinitely miscible with these solvents, such asalcohols, dimethylformamide, dimethylacetamide, dimethylsulphoxide orsulpholane, and the synthetic fibre materials are impregnated with theresulting clear dyestuff solutions, which can optionally further containsoluble non-ionic auxiliaries, for example the known surfaceactiveoxethylation and propoxylation products of fatty alcohols, alkylphenols,fatty acid amides and fatty acids, in order to improve the uniformity ofthe dyeings. Thereafter the dyestuffs are fixed onto the fibre materialsby a heat treatment. The heat treatment can consist of a brief dry heattreatment at 230C, it being possible for the dry heat treatmentoptionally to be preceded by an intermediate drying, or can consist of atreatment of the fibre materials in superheated solvent vapour atl00l50C. Slight amounts of nonfixed dyestuff can be eluted by brieftreatment with the cold organic solvent. lt should be pointed out thatmixtures of the dyestuffs to be used according to the inventionsometimes provide a better colour yield than the individual dyestuffsand at time show an even better solubility in the organic medium.

With the aid of the process according to the invention it is possible toachieve dyeings from organic solvents onto synthetic fibre materials,which are distinguished by a high dystuff yield, very good build-up andexcellent fastness properties, especially very good fastness tothermofixing, washing, rubbing and light. A further advantage of thedyestuffs to be used according to the invention is their high solubilityin organic solvents, especially in tetrachlorethylene, trichlorethylene,1,1,l-trichlorethane and 1,1 ,l-trichloropropane, which in particularmakes it possible to carry out the dyeing even without the use ofsolubilising agents.

The parts given in the examples which follow are parts by weight.

EXAMPLE 1 l A woven fabric of polyethyleneterephthalate fibres isimpregnated at room temperature with a clear yellowred solution whichcontains parts of 1-amino-2-(4- isooctylphenylthio)-anthraquinone in 990parts of tetrachlorethylene. After squeezing out to a weight inl creaseof 60 percent, the woven fabric is dried for 1 minute at 80C. Thereafterthe dyestuff is fixed by heating the fabric for 45 seconds to 190 220C.Subsequently, the slight amount of non-fixed dyestuff is eluted by brieftreatment in cold tetrachlorethylene for seconds. After drying, a clearyellow-red dyeing is obtained which is distinguished by its highdyestuff yield, very good build-up and excellent fastness properties,especially very good fastness to thermofixing, washing, rubbing andlight.

Equivalent clear yellow-red dyeings were also obtained analogously onwoven fabrics of (a) cellulose triacetate, (b) synthetic polyamides orpolyurethanes and (c) polypropylene fibres; the only difference was thatthe thermosol treatment was carried out at 200 3 220C for a), at 170200C for b) and at 120 150C for c).

Equivalent dyeings were also obtained if the 990 parts oftetrachlorethylene were replaced by the same amount of one of thefollowing solvents: methylene chloride, chloroform, carbontetrachloride, dichlorethane, trichlorethane, trichlorethylene,tetrachlorethane, dichloropropane, I ,1 ,1 -trichloropropane,chlorobutane, dichlorobutane, perfluoro-n-hexane,1,2,2-trifluorotrichlorethane and trifluoropentachloropropane.

The dyestuff used had been manufactured as follows:

Twenty parts of 2-brom-l-aminoanthraquinone, 5.5 parts of potassiumcarbonate and 17 parts of 4-isooctyl-l -mercapto-benzene were heated tothe boil in parts of dimethylformamid until the dyestuff formation wascomplete. After cooling, the melt was introduced into an ice-watermixture. The precipitated dyestuff was filtered off, washed with waterand dried in air. The dyestuff yield is practically quantitative.

EXAMPLE 2 A knitted fabric of polyhexamethylenediamine adipate filamentsis impregnated at room temperature with a clear red-violet solutionwhich contains 10 parts of 1-amino-2-(4-isooctylphenylthio)-4-hydroxyanthraquinone and 7 parts of nonylphenolheptaglycol-ether in 983parts of tetrachlorethylene. After squeezing out to a weight increase of60 percent the knitted fabric is dried for 1 minute at 80C. Thereafterthe dyestuff is fixed by heating the knitted fabric to 192C for seconds.Small amounts of non-fixed dyestuff are then eluted by brief treatmentin cold tetrachlorethylene for about 20 seconds. After drying, a clearred-violet dyeing is obtained which is distinguished by its highdyestuff yield, very good build-up and excellent fastness properties,especially very good fastness to thermofixing, washing, rubbing andlight.

An equivalent dyeing was also obtained if instead of the 983 parts oftetrachlorethylene the same amount of toluene, xylene, chlorobenzene,dichlorobenzene, fluorobenzene or benzotrifluoride was used.

The dyestuff used had been manufactured as described in Example 1,except that 2l parts of 4- hydroxy-Z-brom-l-amino-anthraquinone wereused instead of 20 parts of 2-brom-l-amino-anthraquinone.

EXAMPLE 3 A woven fabric of polypropylene fibres is impregnated at roomtemperature with a clear red-violet solution which contains 10 parts ofthe dyestuff named in Example 2 and 7 parts ofnonylphenol-heptaglycolether in 983 parts of tetrachlorethylene. Aftersqueezing out to a weight increase of 60 percent, the woven fabric isdried for 1 minute at C. Thereafter the dyestuff is fixed by heating thewoven fabric to C for 30 seconds. Non-fixed amounts of dyestuff can beeluted by a brief treatment in cold solvent. A clear redviolet dyeing isobtained which is distinguished by high dyestuff yield, very goodbuild-up and excellent fastness properties, especially very goodfastness to thermofixing, washing, rubbing and light.

EXAMPLE 4 A woven fabric of poly-l,4-cyclohexanedimethyleneterephthalate is impregnated at room temperature with a clear red-violetsolution which contains 10 parts of l-amino-2-(4-tert.-butylphenylthio)-4- hydroxyanthraquinone and 7 parts of nonylphenylheptaglycol-ether in983 parts of tetrachlorethylene. After squeezing out to a weightincrease of 60 percent, the woven fabric is dried for 1 minute at 80C.Thereafter the dyestuff is fixed by heating the woven fabric to 220C for45 seconds. The small amount of nonfixed dyestuff is then eluted bybrief treatment in cold tetrachlorethylene for 20 seconds. After drying,a clear red-violet dyeing is obtained, which is distinguished by itshigh dyestuff yield, very good build-up and excellent fastnessproperties, especially very good fastness to thermofixing, washing,rubbing and light.

The dyestuff used has been manufactured as follows:

Twenty parts of 4-hydroxy-2-broml aminoanthraquinone, 6 parts ofpotassium carbonate and l 1 parts of 4-tert.-butyl-l-mercapto-benzene in40 parts of dimethylformamide were heated to the boil until the dyestuffformation had ended. After cooling, the melt was introduced into anice-water mixture. The precipitated violet dyestuff powder was filteredoff, washed with water and dried in air. The dyestuff yield ispractically quantitative.

EXAMPLE 5 A woven fabric of cellulose triacetate fibres is impregnatedat room temperature with a clear blue-violet solution which contains 10parts of 1,4-diamino-2-(4- tert.-butylphenylthio)-anthraquinone in 990parts of tetrachlorethylene. After squeezing out to a weight increase of60 percent, the woven fabric is dried for 1 minute at 80C. Thereafterthe dyestuff is fixed by heating the woven fabric to 215C for 1 minute.A clear, strong, reddish-tinged blue dyeing is obtained which isdistinguished by high dyestuff yield, very good build-up and excellentfastness properties, especially very good fastness to thermofixing,washing, rubbing and light.

The dyestuff used had been manufactured as follows:

Twenty parts of 1,4-diamino-2-bromanthraquinone, 6 parts of potassiumcarbonate and 11 parts of 4-tert.- butyl-l-mercapto-benzene in 40 partsof dimethylformamide were heated to the boil until the dyestuffformation had ended. After cooling, the melt was introduced into anice-water mixture. The precipitated reddishtinged blue dyestuff powderwas filtered off, washed with water and dried in air. The dyestuff yieldis practically quantitative.

EXAMPLE 6 A woven fabric of anionically modified polyethyleneterephthalate fibres (Dacron 64) is impregnated at room temperature witha clear blue-violet solution which contains parts of 1,4-diamino-2-(4-methylphenylthio )-anthraquinone and 7 parts of nonylphenol-heptaglycolether in 983 parts of tetrachlorethylene. After squeezing out to aweight increase of 60 percent, the woven fabric is dried for 1 minute at80C. Thereafter the dyestuff is fixed by heating the woven fabric to 190220C for 45 seconds. The small amount of non-fixed dyestuff is theneluted by brief rinsing with cold tetrachlorethylene. After drying, aclear, strong, reddish-tinged blue dyeing is obtained which isdistinguished by its high dyestuff yield, very good build-up andexcellent fastness properties, especially very good fastness tothermofixing, washing, rubbing and light.

EXAMPLE 7 A woven fabric of anionically modified polyamide fibres (NylonT 844) is impregnated at room temperature with a clear blue solutionwhich contains 10 parts of l-amino-2-(4-tert.-butylphenylthio)-4-cyclohexylamino-anthraquinone and 7 parts ofnonylphenol-heptaglycol-ether in 983 parts of tetrachlorethylene. Aftersqueezing out to a weight increase of 60 percent the woven fabric isdried for 1 minute at 80C and the dyestuff is fixed by heating the wovenfabric to 192C for 1 minute. A clear blue dyeing is obtained which isdistinguished by high dyestuff yield, very good build-up and excellentfastness properties, especially very good fastness to thermofixing,washing, rubbing and light.

The dyestuff used had been manufactured as follows:

25.2 parts of lamino-2-bromo-4-cyclohexylaminoanthraquinone, 6 parts ofpotassium carbonate and 11 parts of 4-tert.-butyl-l-mercapto-benzene in45 parts of dimethylformamide were heated to the boil until the dyestuffformation had ended. After cooling, the melt was introduced into anice-water mixture. The precipitated blue dyestuff powder was filteredoff, washed with water and dried in air. The dyestuff yield is almostquantitative.

EXAMPLE 8 A woven fabric of polyethylene terephthalate fibres isimpregnated at room temperature with a clear blue solution whichcontains 5 parts of 1,4-diamino-2-(4-tert.-butylphenylthio)-anthraquinone and 5 parts oflamino-2-(4-tert.-butylphenylthio)-4-(4-methylphenylamino)-anthraquinone in 990 parts of 1,1,l-trichlorethane.After squeezing out to a weight increase of 60 percent the dyestuff isfixed by treating the woven fabric with superheated 1,1,l-trichlorethane vapour at 140C for 45 seconds. Thereafter the smallamount of non-fixed dyestuff is eluted by brief rinsing in cold 1,1,l-trichlorethane. After drying, a reddishtinged blue dyeing is obtainedwhich is distinguished by its high dyestuff yield, very good build-upand excellent fastness properties.

EXAMPLE 9 A woven fabric of poly-l,4-cyclohexanedimethyleneterephthalate is impregnated at room temperature with a clear red-violetsolution which contains 10 parts oflamino-2-(4-iso-propylphenylthio)-4-hydroxyanthraquinone in 990 parts oftetrachlorethylene. After squeezing out to a weight increase of percentthe dyestuff is fixed by treating the woven fabric with superheatedtetrachlorethylene vapour at C for 35 seconds. The small amount ofnon-fixed dyestuff is then eluted by brief rinsing in coldtetrachlorethylene. After drying, a clear red-violet dyeing is obtainedwhich is distinguished by its high dyestuff yield, very good buildup andexcellent fastness properties.

Strong dyeings on woven fabrics of polyester, triacetate, polyamide,polyurethane and polyolefin fibres, having excellent fastnessproperties, were also obtained if instead of the dyestuffs indicated inExamples 1 9 the same amount of one of the dyestuffs indicated in thetable below was used. The resulting colour shades are given in the lastcolumn.

Example Dyestuff Colour Shade 10 l-amino-2-( 4-tert.-butylphenylthioanthraquinone yellowred 1 l 1-amino-2-(2,6-diethylphenylthio)-anthraquinone yellow-red 12 l-amino-2-( 4-cyclohexylphenylthio)-anthraquinone yellow-red l3 l-amino-2-(2-cyclohexylphenylthio)-anthraquinone yellow-red l4 l-amino-2-(4-methylphenylthio)-anthraquinone yellow-red 15 1-amino-2-(2-methylphenylthio)-4-hydroxy-anthraquinone rcd-vio|et l6 l-amino-2-(4-isononylphenylthio)-4-hydroxy-anthraquinone red-violet l7 l-amino-2-(4-cyclohexylphenylthio)-4- hydroxy-anthraquinone red-violet l8l-amino-2-(2-cyclohexylphenylthio)-4- hydroxy-anthraquinone red-violet19 l-amino-2-(4-isohexylphenylthio)-4- hydroxy-anlhraquinone red-violet20 l-amino-2-( 3 ,5-diisopropylphenylthio)- 4-hydroxy-anthraquinonered-violet 21 1-amino-2-(4-isoamylphenylthio)- 4- hydroxy-anthraquinonered-violet 22 l-amino-2-(4-benzylphenylthio )-4- hydroxy-anthraquinonered-violet 23 l-amino-2-l 4-( 2-phenylpropyl-( 2phenylthiol-4-hydroxy-anthraquinone red-violet 24l-amino-Z-(4-cyclohexyl-Z-methylphenylthio-4-hydroxy-anthraquinonered-violet 25 l-amino-2-( 2,4,6-triethylphenylthio)-4-hydroxy-anthraquinone red-violet 26l-amino-2-(4-chlor-3-isooctylphenylthio )-4-hydroxy-anthraquinonered-violet 27 l-amino-2-( 2-brom-4-isooctylphenylthio)-4-hydroxy-anthraquinone red-violet 28 l-amino-2-(2,6-dichlor-4-isononylphenylthio )-4-hydroxy-anthraquinone red-violet 29l-amino-2-(2,6-dibrom-4-isooctylphenylthio)-4-hydroxy-anthraquinonered-violet 30 1 -amino-2-( 4-tert.-butylphenylthio4-methoxy-anthraquinone yellow-red 31 1-amino-2-( 4-ethylphenylthio )-4-ethoxy-anthraquinone yellow-red 32l-amino-2-(4-methylphenylthio)-4-npropoxy-anthraquinone yellow-red 331-amino-2-(2-methylphenylthio)-4-nbutoxy-anthraquinone yellow-red 341,4diamino-2-(4-isooctylphenylthio reddish-tinged anthraquinone blue 35l,4-diamino-2-( Z-methylphenylthio reddish-tinged anthraquinone blue 361,4-diamino-2-isopropylphenylreddish-tinged thio )-anthraquinone blue 37l,4-diamino-2-(4-cyclohexylphenylreddish-tinged thio)-anthraquinone blue38 l,4-diamino-2-(4-benzylphenylthio)- reddish-tinged 7 anth raquinoneblue 39 l ,4-diarnino-2-l 4-( 2-phenylpropyI-( 2 reddish-tingedphenylthiol-anthraquinone blue 40 l-amino-2-( 4tert.-butylphenylthio)-4-methylaminoanthraquinone blue 4 l l-amino-2-(4-methylphenylthio )-4-ethylaminoanthraquinone blue 42 l-amin-2-(Z-methylphenylthio)-4-nbutylamino-anthraquinone blue 43 l-amino-2-( 4-methylphenylthio)-4- cyclohexylamino-anthraquinone blue 44 l-amino-2-(4-tert.-butylphenylthio )-4- (4-methylcyclohexylamino)-anthraquinone blue 45 l-arnino-2-( 2-methylphenylthio)-4-(2,4,-trimethylcyclohexylamino blue anthraquinone 46l-an1ino-2-(4-tert.-butylphenylthio)-4- (4-chlorophenylamino)-anthraquinone blue 47 l -amino-2-(4-isooctylphenylthio )-4-(3-bromophenylamino )-anthraquinone blue 48l-amino-2-(4-isononylphenylthio )-4- (2,5-dichlorophenylamino)-anthraquinone blue 49 l -amino-2-(4-isooctylphenylthio)-4-(3-trifluoromethylphenylamino)-anthrablue quinone 50l-amino-2-(4-isopropylphenylthio)-4-(4- fluorophenylamino)-anthraquinoneblue 51 l -amino-2-(4-tert.-butylphenylthio 4-tosylamino-anthraquinoneviolet 52 l-amino-2-(4-isooctylphenylthio 4-tosylamino-anthraquinoneviolet 53 l-arnino-2-(4-isononylphenylthio )-4-phenylsulphonylamino-anthraquinone violet 54l-amino-2-phenylthio-4-(4-tert.-

butylphenylamino)-anthraquinone blue 55 l-amino-2-(4-methylphenylthio)-4- reddish-tinged (2-ethylphenylarnino)-anthraquinone blue 56l-amino-2-(4-tert.-butylphenylthio )-4- reddish-tinged(2,6-dimethylphenylamino)-anthraquinone ue 57l-amino-2-(2-methylphenylthio )-4-( 2- reddish-tingedisopropylphenylamino )-anthraquinone blue 58l-amino-2-(4-melhylphenylthio )-4- (2,3,5-trimethylphenylamino)-anthrareddish-tinged quinone blue 59l-arnino-2-(4-methylphenylthio)-4(4- n-butylphenylamino)-anthraquinoneblue 60 l-amino2-phenylthio4-(4-isooctylphenylamino )-anthraquinone blue6 l l-amino-2-(4-n-butylphenylthio)-4- reddish-tinged2,4,6-triethylphenylamino)-anthrablue quinone 62l-amin0-2-(4-isooctylphenylthio)-4- [3,5-bis-(trifluoromethyl)-phenylblue amino l anthraquinone 63 l-amino-2-(4-methylphenylthio )-4- (4- cyclohexylphenylamino)-anthraquinone blue 64l-amino-2-( 2-methylphenylthio )-4-( 2- methyl-4-cyclohexylphenylaminoreddish-tinged anthraquinone blue 65l-amino-2-(4-tert.-butylphenylthio)-4- ,6,7,8-tetrahydro-Z-naphthylaminoanthraquinone blue 66 l-amino-2-(4-tert.-butylphenylthio 4-(S,6,7,8-tetrahydrol naphthylamino)- reddish-tinged anthraquinone blue 67l-amino-2-( 4-tert.-butylphenylthio 4-(4-rnethoxyphenylamino)-anthraquinone blue 68l-amino-2-(4-tertpbutylphenylthio)-4-(2,4-dimethoxyphenylamino)-anthraquinone blue 69l-amino-2-(4-isooctylphenylthio)-4- (4-ethoxyphenylamino)-anthraquinoneblue 70 l-amino-2-phenylthio-4-( 4-isoamyloxyphenylamino)-anthraquinoneblue 71 l-amino-2-(4-methylphenylthio)-4-(3-isobutoxyphenylamino)-anthraquinone blue 72l-arnino-2-(2-methylphenylthio)-4-(4-npropoxyphenylamino )-anthraquinoneblue 73 l-amino-2-phenylthio-4-( S-isoamyloxyphenylamino)-anthraquinoneblue 74 1-amino-2-(4-tert.-butylphenylthio)-4-(2,5-diethoxyphenylarnino)-anthraquinone blue 75l-amino-2-(4-tert.-butylphenylthio)-4- (4-fi-methoxyethoxyphenylamino)-anthraquinone blue 76 l-amino-2-(4-rnethylphenylthio )-4-(4-nbutoxyphenylamino )-anthraquinone blue 77l-amino-2-(4-tert.-butylphenylthio)-4- (3,Ldimethoxyphenylamino)-anthraquinone 1 blue 7 8 Il-amino-2-phenylthio-4-( 4-isooctyloxy- I phenylamino) aiitln'aquinone rblue 79 l-amino-2-phenylthio-4-[4 (2.2-dimethylbutoxyl-phenylaminolanthraquinone blue 80l-amino-2-phenylthio-4-[3-(2-ethylhexoxyl-phenylaminol-anthraquinoneblue 8! l-amino-2 (4-isooctylphenylthio)- 54-methylsulphonylamino-anthraquinone violet 82 l-amino-2-(4-isooctylphenylthio)- 4-ethylsulphonylarnino-anthraquinone violet 8 3l-amino-2-( Z-isopropyl-Zl-methylphenylthio)-anthraquinone yellow-red 84l-arnino-2-(2-isopropyl-3-methylphenylthio)-4-hydroxy-anthraquinonered-violet 85l-amino-2-(2-isopropyl-4-methylphenylthio)-4-hydroxy-anthraquinonered-violet 86 l,4-cliamino-2-(2isopropyl-3-methylreddish-tingedphenylthio)-anthraquinone blue 87 l-amino 2-(2-isopropyl-3-methylphenylthio)-4 (methyl-phenyiamino)- anthraquinoneblue 88l-amino-2-(2-isopropyl-3-methylphenylthio)-4-tosylamino-anthraquinoneviolet We claim: 1. Process for the continuous dyeing of syntheticpolyester fiber material comprising the steps of A. impregnating thefiber material with a nonaqueous dyeing liquor said liquor consistingessentially of an organic solvent and an anthraquinone dyestufflsaidorganic solvent consisting of waterimmiscible halogenated hydrocarbonboiling between and 150C, said anthraquinone dyestuff having the formuladroxyl, lower alkoxy, amino, lower alkylamino, cycloalkylamino,arylamino substituted by halogen or trifluoromethyl, arylsulfonylamino,alkyl-sulfonylamino,

m is a number from 0-2;

n is a number from 0-3;

p is a number from 0-3;

q is a number from 0-2;

B and B independently of one another are C -C alkyl, cycloalkyl oraralkyl; with the proviso that the sum of the carbon atoms present inthe substituent B or the substituents B and B is l to 9; the sum of nand p and q is at least 1; and

B. subjecting the fiber material to a heat-treatment to fix saiddyestuff on said fiber material.

2. The process of claim 1 in which said anthraquinone dyestuft has theformula in which B is C C -alkyl-, cycloalkylor aralkyl.

3. The process of claim 1 in which said anthraquinone dyestuff has theformula i 0 NH,

in which B is C C -alkyl, cycloalkyl or aralkyl.

4. The process of claim 1 in which said anthraquinone dyestufi' has theformula (B), ll l S I)I Nil-55 O1-R in which B is C C -alkyl, cycloalkylor aralkyl; R is phenyl, phenyl substituted with lower alkyl or loweralkyl. I

6. The process of claim 1 in which said anthraquinone dyestuff issoluble in said water-immiscible halogenated hydrocarbon.

7. The process of claim 6 in which the dyed material is subjected to asubsequent step of (C) rinsing with water-immiscible organic solvent inwhich said anthraquinone dyestuff is soluble.

8. The process of claim 1 in which said waterimmiscible halogenatedhydrocarbon is an aliphatic chlorohydrocarbon having a boiling point ofbetween 40 and 150C.

9. The process of claim 1 in which said waterimmiscible organic solventis selected from the group consisting of tetrachloroethylene,trichloroethylene, l,l,l-trichloroethane, 1,1,1-trichloropropane andmixtures thereof.

10. The process of claim 1 in which said heat treatment is conductedunder dry heat conditions at a temperature of l20230C.

11. The process of claim 1 in which said heat treatment is conducted insuperheated solvent vapor at 12. The dyed fiber produced by the processof claim 1.

2. The process of claim 1 in which said anthraquinone dyestuff has theformula
 3. The process of claim 1 in which said anthraquinone dyestuffhas the formula
 4. The process of claim 1 in which said anthraquinonedyestuff has the formula
 5. The process of claim 1 in which saidanthra-quinone dyestuff has the formula
 6. The process of claim 1 inwhich said anthraquinone dyestuff is soluble in said water-immisciblehalogenated hydrocArbon.
 7. The process of claim 6 in which the dyedmaterial is subjected to a subsequent step of (C) rinsing withwater-immiscible organic solvent in which said anthraquinone dyestuff issoluble.
 8. The process of claim 1 in which said water-immisciblehalogenated hydrocarbon is an aliphatic chlorohydrocarbon having aboiling point of between 40 and 150*C.
 9. The process of claim 1 inwhich said water-immiscible organic solvent is selected from the groupconsisting of tetrachloroethylene, trichloroethylene,1,1,1-trichloroethane, 1, 1,1-trichloropropane and mixtures thereof. 10.The process of claim 1 in which said heat treatment is conducted underdry heat conditions at a temperature of 120*-230*C.
 11. The process ofclaim 1 in which said heat treatment is conducted in superheated solventvapor at 100*-150*C.
 12. The dyed fiber produced by the process of claim1.